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WO2005028101A1 - Procede de production de catalyseurs d'oxyde de silicium contenant du titane, catalyseurs ainsi obtenus et procede de production d'oxiranes a l'aide de tels catalyseurs - Google Patents

Procede de production de catalyseurs d'oxyde de silicium contenant du titane, catalyseurs ainsi obtenus et procede de production d'oxiranes a l'aide de tels catalyseurs Download PDF

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Publication number
WO2005028101A1
WO2005028101A1 PCT/JP2004/013584 JP2004013584W WO2005028101A1 WO 2005028101 A1 WO2005028101 A1 WO 2005028101A1 JP 2004013584 W JP2004013584 W JP 2004013584W WO 2005028101 A1 WO2005028101 A1 WO 2005028101A1
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WO
WIPO (PCT)
Prior art keywords
group
titanium
containing silicon
silicon oxide
catalyst
Prior art date
Application number
PCT/JP2004/013584
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English (en)
Japanese (ja)
Inventor
Jun Yamamoto
Original Assignee
Sumitomo Chemical Company, Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2003325736A external-priority patent/JP2005087905A/ja
Priority claimed from JP2003325737A external-priority patent/JP2005089377A/ja
Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Publication of WO2005028101A1 publication Critical patent/WO2005028101A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/34—Reaction with organic or organometallic compounds

Definitions

  • the present invention relates to a method for producing a titanium-containing silicon oxide catalyst, a method for producing the catalyst and an oxirane compound using the catalyst.
  • the present invention relates to a method for producing an oxysilane compound. More specifically, the present invention relates to a propylene oxide in which an olefin compound such as propylene is reacted with a hydroperoxide using a titanium-containing silicon oxide catalyst prepared by a non-hydrolytic condensation reaction in the absence of water. The present invention relates to a method for producing an oxysilane compound such as a side. Background art
  • An object of the present invention is to provide an olefin-type compound and a hydroperoxide using a catalyst obtained by subjecting a titanium-containing silicon oxide prepared by a non-hydrolytic condensation reaction to a silylation treatment in a liquid phase in the absence of water. Oxilla with high yield It is an object of the present invention to provide a method for producing an oxysilane compound capable of obtaining a halogenated compound.
  • the present invention provides a method of performing a silylation treatment on a titanium-containing silicon oxide prepared by a non-hydrolytic condensation reaction represented by the following formula (I) in a liquid phase in the absence of water.
  • the present invention relates to a method for producing a titanium-containing silicon oxide catalyst, and a method for producing an oxysilane compound characterized by reacting an olefin compound with hydroperoxide in the presence of the catalyst.
  • M is S i or T i
  • X is a halogeno group or a carboxy group and R is a hydrogen or hydrocarbon group
  • 1 ⁇ to 6 are each independently an alkoxy group, a halogeno group, a carpoxy group, Represents a hydrogen or hydrocarbon group.
  • Another object of the present invention is to react propylene with a peroxide at a port opening using a titanium-containing silicon oxide catalyst prepared by a non-hydrolytic condensation reaction in a liquid phase in the absence of water.
  • An object of the present invention is to provide a method for producing propylene oxide, which can obtain propylene oxide with a high yield.
  • the present invention provides propylene and hydroperoxide in the liquid phase in the absence of water in the presence of a titanium-containing silicon oxide catalyst prepared by a non-hydrolytic condensation reaction represented by the following formula (I).
  • a method for producing propylene oxide by reacting oxide is provided.
  • the catalyst is obtained by subjecting a titanium-containing silicon oxide prepared by a non-hydrolytic condensation reaction represented by the following formula (I) to a silylation treatment in a liquid phase in the absence of water. can get.
  • M is S i or T i
  • X is a halogeno group or a carboxy group and R is a hydrogen or hydrocarbon group
  • 1 ⁇ to 1 ⁇ 6 are each independently an alkoxy group, a halogeno group, a carboxy group. Represents a group, hydrogen or a hydrocarbon group.
  • a silica source and a titanium source are gelled by a non-hydrolytic condensation reaction represented by the above formula (I) in a liquid phase to obtain a wet gel of a titanium-containing silicon oxide.
  • a silicon compound represented by the following formula (1) can be preferably mentioned.
  • Fluorine examples of X 1, chlorine, bromine, and a carboxy group such as a halogeno group Ya Asetokishi group iodine are exemplified, and among them, chlorine is preferred.
  • R 1 examples include hydrocarbon groups such as methyl, ethyl, propyl, isopropyl, and petyl (which may contain heteroatoms such as oxygen and nitrogen).
  • An isopropyl group is preferred from the viewpoint of the conversion rate.
  • R 2 examples include hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, phenyl group and benzyl group (which may contain hetero atoms such as oxygen and nitrogen). Can be.
  • the silicon compound examples include silicon tetrachloride, tetraisopropoxysilane, methyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane.
  • silicon compounds it is preferable to prepare a gel containing tetrahalogenosilane and / or tetraalkoxysilane as a main component from the viewpoint of strengthening the gel structure and stabilizing the structure.
  • titanium source used here a titanium compound represented by the following formula (2) can be preferably mentioned.
  • Fluorine examples of X 2 chlorine, bromine, although halogeno groups iodine and the like, and among them, chlorine is preferred.
  • R 3 and R 4 include a hydrocarbon group having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a phenyl group (a heteroatom such as oxygen and nitrogen). May be included).
  • titanium compounds include halogeno-titanium such as titanium tetrachloride, titanium ethoxide, titanium isopropoxide, titanium isobutoxide, titanium mono-butoxide and the like titanium alkoxide, titanium diisopropoxide (bis-2 , 4-pennionate) and the like.
  • halogeno-titanium such as titanium tetrachloride, titanium ethoxide, titanium isopropoxide, titanium isobutoxide, titanium mono-butoxide and the like titanium alkoxide, titanium diisopropoxide (bis-2 , 4-pennionate) and the like.
  • the above-mentioned silica source and titanium source are mixed and used.
  • One or more of the silica source and the titanium source may be used, respectively.
  • a non-aqueous solvent may or may not be used. It is important that the non-aqueous solvent does not substantially contain water, and specific examples include alcohols, ethers, hydrocarbons, and halogenated hydrocarbons. They can also be used as a mixture.
  • the added non-aqueous solvent may react with the above-mentioned silicon source and titanium source.
  • a structure-directing agent such as a primary to tertiary amine / quaternary ammonium ion or a surfactant may or may not be used.
  • the amount of the titanium source to be used relative to the Si force source is usually 10 5 to 1, and preferably 0.000 to 0.4 in a molar ratio. More preferably, it is 0.01 to 0.1.
  • the gelation temperature is usually ⁇ 30 to 200 ° C., but the heating promotes the gelation. In the case of heating, it is preferable that the heating is performed by transferring to a pressure-resistant container and sealing in order to avoid vaporization of the silica source, the titanium source and the non-aqueous solvent.
  • the wet gel obtained by the above method contains RX and / or a non-aqueous solvent described in the above formula (I), it is removed by drying to obtain a titanium-containing silicon oxide. Drying is performed at 0 to 200 ° C. under reduced pressure or under a flow of gas such as nitrogen.
  • the wet gel obtained by non-hydrolytic condensation has only a small capillary force during drying, and only the RX and / or non-aqueous solvent described in the above formula (I) is removed.
  • a titanium-containing silicon oxide having a large pore volume is obtained.
  • the specific surface area is preferably not less than 2 0 O mV g, 4 0 0 m 2 / g or more is more preferable.
  • the specific pore volume is preferably 0.2 m 1 / g or more.
  • propylene oxide By reacting propylene with hydroperoxide using the titanium-containing silicon oxide obtained by the above method as a catalyst, propylene oxide can be obtained in high yield.
  • a treatment is applied.
  • the silylation treatment is performed by bringing the titanium-containing silicon oxide obtained by the non-hydrolytic condensation reaction into contact with a silylating agent and converting the halogeno group ⁇ alkoxy group remaining on the catalyst surface into a silyl group.
  • the silylating agent include organic halogenosilanes, organic silylamines, organic silylamides and derivatives thereof, and organic silazanes.
  • the silylation treatment may be performed in the gas phase, It may be performed in the liquid phase.
  • a solvent may or may not be used.
  • the treatment temperature is not particularly limited, but is preferably in the range of 0 ° C to 200 ° C.
  • the contact time is not particularly limited, it is preferably 10 minutes to 10 hours.
  • the silylation treatment may be performed after the wet gel is dried, or may be performed before the drying or simultaneously with the gel preparation.
  • the catalyst obtained by the above method can be optimally used particularly for a method for producing an oxysilane compound by reacting an olefin compound with a hydroperoxide.
  • the olefin type compound may be an acyclic, monocyclic or polycyclic olefin compound, and may be a monoolefin type, a diolefin type or a polyolefin type having three or more double bonds. When there are two or more olefin bonds, these may be a conjugate bond or a non-conjugate bond.
  • Olefin type compounds having 2 to 60 carbon atoms are generally preferred. Although it may have a substituent, the substituent is preferably a relatively stable group.
  • Examples of monoolefin hydrocarbons include ethylene, propylene, 1-butene, isobutylene, 1-hexene, 2-hexene, 3-hexene, 1-octene, 1-decene, styrene, cyclohexene, etc.
  • suitable diolefin type compounds include butadiene and isoprene. When it has a substituent, examples thereof include a halogen atom, and further, various substituents containing an oxygen, sulfur, or nitrogen atom together with a hydrogen and / or a carbon atom may be used.
  • Particularly preferred substituted olefinic compounds are olefinic unsaturated alcohols, and olefinic unsaturated hydrocarbons substituted with octogen, examples of which include aryl alcohol, crotyl alcohol, and aryl chloride. .
  • Particularly preferred as olefin-type compounds are those having 3 to 40 carbon atoms, which may be substituted by hydroxyl groups or halogen atoms.
  • Hydroperoxides used for converting an olefin type compound to an oxysilane compound include organic hydroperoxides and hydrogen peroxide, and organic hydroperoxides are preferred.
  • organic hydroperoxides include cumene hydroperoxide, ethylbenzene hydroperoxide, and tributyl octyl peroxide. Most preferred is cumene hydroperoxide.
  • the organic hydroperoxides and hydrogen peroxide used may be dilute or rich purified or unpurified products.
  • the reaction can be carried out in the liquid phase in the presence or absence of a solvent.
  • the solvent is liquid at the temperature and pressure during the reaction and is substantially inert to the reactants and products.
  • the solvent may consist of substances present in the hydroperoxide solution used. For example, when cumene hydroperoxide is a mixture of cumene hydroperoxide and its raw material, cumene, it can be used in place of a solvent without adding a solvent. It is.
  • the reaction temperature is generally between 0 and 200 ° C, preferably between 25 and 200 ° C.
  • the pressure may be sufficient to keep the reaction mixture in a liquid state. In general, it is advantageous for the pressure to be between 100 and 1000 kPa.
  • the amount of the olefin-type compound (mole number) relative to the hydroperoxide (mole number) in the reaction is not limited, but is usually 1 or more, preferably 1 to 50 times by mol, in a molar ratio.
  • the process of the invention can be carried out in the form of a slurry, fixed bed. This reaction can be carried out by a batch method, a semi-continuous method or a continuous method.
  • titanium isopropoxide, tetrisopropoxysilane and silicon tetrachloride were added to a pressure-resistant ampoule at a molar ratio of 1.0: 4.5: 5.5, mixed and sealed.
  • the content weight was 17.6 g.
  • the mixture was heated in an oven at 110 ° C. for 4 days to gel. After opening the wet gel under vacuum at 150 ° C for 4 hours Drying for 6. lg of dried gel was obtained. The resulting red-brown dried gel was ground using a mortar to obtain a titanium-containing silicon oxide (powder). This was used as a catalyst.
  • the catalyst obtained as described above was reacted with a cumene solution having a concentration of 25% by weight of cumene hydride (CHPO) and propylene in a reactor (autoclave) to synthesize and evaluate propylene oxide.
  • CHPO cumene hydride
  • the autoclave was charged with 30 g of a solution of lg, CHPO in cumene of CHPO, and 17 g of propylene, and reacted under autogenous pressure at a reaction temperature of 85 ° (with a reaction time of 1.5 hours (including a heating time).
  • the results are shown in Table 1.
  • Example 2 Example 2
  • Propylene oxide was produced in the same manner as in the synthesis of propylene oxide in Example 3, except that the catalyst obtained in the above catalyst preparation was used. As a result, the CHP ⁇ conversion was 89.0%, and the selectivity for PO / C 3 ′ was 99.2%.
  • Example 5
  • titanium tetrachloride, silicon tetrachloride, trimethylchlorosilane, trimethylchlorosilane, and diisopropyl ether are added in a pressure-resistant ampoule in a molar ratio of 1.0: 6.0: 2.0: 2.0: 18.0.
  • 15 ml of dichloromethane as a solvent was mixed and sealed. The content weight was 44.4 g. Heated in an oven at 110 to gel. After opening, the wet gel was dried under vacuum at 150 ° C. for 4 hours to obtain 5.9 g of a dry gel. The resulting yellow-brown dried gel was ground using a mortar to obtain a titanium-containing silicon oxide (powder).
  • Propylene oxide was produced in the same manner as in the synthesis of propylene oxide in Example 3, except that the catalyst obtained above was used. As a result, the CHPO conversion was 43.6%, PO / C3, and the selectivity was 92.4%.
  • Propylene oxide was produced in the same manner as in the synthesis of propylene oxide in Example 3, except that the catalyst obtained above was used. As a result, the CHPO conversion was 72.8%, PO / C3, and the selectivity was 99.6%. Industrial applicability
  • the present invention can be used in a reaction for obtaining an oxysilane compound from a olefin compound such as propylene and a hydroperoxide. Accordingly, it is possible to provide a method for producing a titanium-containing silicon oxide catalyst capable of exhibiting a high yield, and an efficient method for producing an oxysilane compound using the catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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  • Epoxy Compounds (AREA)

Abstract

Cette invention concerne un procédé permettant de produire des catalyseurs, lequel procédé se caractérise par une étape consistant à soumettre un oxyde de silicium contenant du titane, préparé dans une phase liquide en l'absence d'eau par condensation non-hydrolytique et représenté par la formule de réaction (I), à une silylation. L'invention concerne également un procédé permettant de produire des oxiranes par réaction d'un composé oléfinique avec un peroxyde d'hydrogène en présence d'un catalyseur produit selon le procédé susmentionné: (I) L1L2L3M-X+L4L5L6M-OR → L1L2L3M-O-ML4L5L6+RX, dans cette formule, M représente Si ou Ti; X représente halogéno ou carboxy; R représente hydrogène ou hydrocarbyle; et L1 à L6 sont indépendamment les uns des autres alkoxy, halogéno, carboxy, hydrogène, ou hydrocarbyle.
PCT/JP2004/013584 2003-09-18 2004-09-10 Procede de production de catalyseurs d'oxyde de silicium contenant du titane, catalyseurs ainsi obtenus et procede de production d'oxiranes a l'aide de tels catalyseurs WO2005028101A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2003-325736 2003-09-18
JP2003-325737 2003-09-18
JP2003325736A JP2005087905A (ja) 2003-09-18 2003-09-18 チタン含有珪素酸化物触媒の製造方法およびオキシラン化合物の製造方法
JP2003325737A JP2005089377A (ja) 2003-09-18 2003-09-18 プロピレンオキサイドの製造方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2941944A1 (fr) * 2009-02-12 2010-08-13 Sumitomo Chemical Co Procede pour produire de l'oxyde de propylene
FR2941945A1 (fr) * 2009-02-12 2010-08-13 Sumitomo Chemical Co Procede pour produire de l'oxyde de propylene
US7989030B2 (en) * 2006-08-04 2011-08-02 Dow Corning Corporation Silicone resin and silicone composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001031662A (ja) * 1999-07-14 2001-02-06 Sumitomo Chem Co Ltd プロピレンオキサイドの製造方法
JP2002514218A (ja) * 1997-05-05 2002-05-14 アルコ ケミカル テクノロジー，エル．ピー． 改良された不均一触媒組成物を用いるエポキシ化法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002514218A (ja) * 1997-05-05 2002-05-14 アルコ ケミカル テクノロジー，エル．ピー． 改良された不均一触媒組成物を用いるエポキシ化法
JP2001031662A (ja) * 1999-07-14 2001-02-06 Sumitomo Chem Co Ltd プロピレンオキサイドの製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7989030B2 (en) * 2006-08-04 2011-08-02 Dow Corning Corporation Silicone resin and silicone composition
FR2941944A1 (fr) * 2009-02-12 2010-08-13 Sumitomo Chemical Co Procede pour produire de l'oxyde de propylene
FR2941945A1 (fr) * 2009-02-12 2010-08-13 Sumitomo Chemical Co Procede pour produire de l'oxyde de propylene

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